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Hybrid water electrolysis (HyWES) with iodide oxidation as non-OER for energy-saving H2 production is demonstrated using self-supported sulfate ion modified Ni,Fe(oxy)hydroxide as the anode. The sulfate ions adsorbed on the catalyst show a promoting effect in achieving high electrochemical activity. The HyWES requires a voltage as low as 1.36 V to achieve the bechmark current density of 10 mA cm−2. [ABSTRACT FROM AUTHOR]

Since 2006, with the development of an optimized methodology for silicon purification based on alkaline fusion followed by cation-exchange chromatography, silicon isotopes have been widely measured across diverse sample types. Nevertheless, this technique does not remove anions and dissolved organic carbon (DOC), leading to potential matrix effects. Notably, under dry plasma conditions, several studies have reported offset in the δ30Si value up to +1.4‰ when [S]/[Si] > 0.02 (wt/wt) and +0.65‰ when [DOC]/[Si] > 1.75. Here, we examine the matrix effects induced by chloride, sulfate and dissolved organic carbon under wet plasma conditions. To achieve this, we doped the NBS-28 (NIST® RM 8546) solution, with varying amounts of sulfate and chloride and measured the δ30Si value in the doped solutions. To investigate the DOC matrix effect, we used the UV photolysis method to decompose the DOC within natural samples and then compared the resulting δ30Si values with those of untreated samples. Importantly, we did not observe any significant δ30Si offset outside the range of our long-term analytical precision (±0.11‰, 2SD) attributed to chloride, sulfate, or DOC across a range of [Cl−]/[Si] = 0.09 to 5.65, [SO42−]/[Si] = 0.09 to 5.65 and [DOC]/[Si] = 0.08 to 6.38. Even though no offset in δ30Si value is observed for DOC-contaminated samples, we recommend removal of DOC. We suggest that the matrix effect observed under dry plasma conditions can be primarily attributed to the use of introduction systems with desolvating membranes, followed by differences in the operating parameters and the absolute quantity of anions introduced into the plasma. Our study indicates that precise and accurate measurements (<0.11‰, 2SD) can be reached for stable Si isotope ratios by MC-ICP-MS in wet plasma, with a larger tolerance to sample based-matrix effect induced by anion contamination compared to dry plasma. [ABSTRACT FROM AUTHOR]

Na0.4MnO2 microrods were synthesized to adsorb 100 ppm of SO2 and NO2 at room temperature with the maximum uptake capacity of 78.7 and 42.3 mg g−1, respectively. While SO2 was oxidized to sulphate and bisulphate ions, NO2 was converted to nitrite and nitrate ions via hydroxyl groups and Mnn+ redox cycles. [ABSTRACT FROM AUTHOR]

Na2EDTA is an effective morphology regulator in preparing α-calcium sulfate hemihydrate (α-HH) with high mechanical strength, but its simultaneous effect on the phase transformation process and morphology evolution of α-HH is still unclear. This study finds that the addition of Na2EDTA from 0.00 to 1.40 mM dramatically prolongs the induction time and phase transformation time from 2 to 240 min and 118 to 480 min respectively, due to the complexation of Ca2+ and EDTA2− in solution while further increase to 2.20 mM doesn't continuously increase the induction time and phase transformation time. Meanwhile, the addition of Na2EDTA generates the morphology evolution of α-HH from fibrous to short columnar with an average aspect ratio from 31.5 to 1.7, resulting from the selective adsorption of EDTA2− on both the top and side faces of α-HH crystals where Ca2+ ions are distributed at different densities. This selective adsorption provides more details compared with the conventional understanding of EDTA2− adsorption focusing on the top faces. Altogether, this work gives a clear view of the relationship between Na2EDTA concentration and phase transformation and morphology evolution of α-HH, which contributes to providing theoretical guidance on preparing α-HH crystals with an appropriate phase transformation rate and ideal morphology. [ABSTRACT FROM AUTHOR]

We successfully synthesized a one-dimensional cobalt sulfate coordinating polymer, whose simple hydrogen bond web structure facilitated the analysis of the proton transfer process. At 175 °C, without humidity, the conductivity is 0.0311 S cm−1, which exceeds those of most of the organic inorganic hybrid materials under anhydrous conditions (world record rank 8). Based on its crystal structure and theoretical calculations, the subversive proton conduction pathway was inferred clearly. We, for the first time, found that the proton smartly chose the path with a lower energy barrier but not the one with short distance to transport avoiding short circuit. [ABSTRACT FROM AUTHOR]

Anions play a significant role in the construction of metal–organic frameworks (MOFs). Anions can affect coordination between metal ions and organic ligands, and the formation of crystal structures, thereby affecting the structure and properties of MOFs. Two novel 3D porous MOFs ({[Cd3(TIPE)2(SO4)1.6(H2O)2.4]·2.8OH·6.2H2O}n (MOF-1) and {[Cd3(TIPE)2(SO4)3(H2O)2]·10H2O}n (MOF-2)) were successfully synthesized, by introducing SO42− to design and adjust their structure and properties, in which the sulfate ions not only participated in coordination but also played a bridging role. Both MOF-1 and MOF-2 exhibited high stability and strong fluorescence properties, and their fluorescence properties also changed compared to those of previously reported 2D nonporous MOF-3 ({[Cd2(TIPE)2Cl3(ACN)]·CdCl3·3H2O}n) with an identical ligand. They could also be used in combination with MOF-3 to distinguish between Fe3+ and Cr2O72− ions, due to a change in their fluorescence properties. In this work, the structure was reshaped by introducing sulfate ions, and the role and function of the sulfate ions in the structure were studied, providing a feasible idea for the design and precise regulation of MOFs. [ABSTRACT FROM AUTHOR]

It has been proved that the removal of aromatic contaminants from the environment with sulfate radical anion (SO4˙−)-based advanced oxidation technology is an effective method. Thus, knowing the second-order rate constants between aromatic contaminants and a sulfate radical is important for evaluating the advanced oxidation processes. In the present manuscript, the quantitative structure–property relationship (QSPR) technique using the inbuilt Monte Carlo algorithm of CORAL software is employed to model the second-order rate constants of the sulfate radical for a dataset of 88 aromatic contaminants. The dataset is used to construct ten random splits and each of them is divided into four sets (i.e. active training, passive training, calibration, and validation). To construct QSPR models, a hybrid optimal descriptor is applied using a combination of SMILES and HFG (hydrogen-filled graph). Four target functions i.e. TF0 (WIIC = WCII = 0), TF1 (WIIC = 0.5 and WCII = 0), TF2 (WIIC = 0 and WCII = 0.3) and TF3 (WIIC = 0.5 and WCII = 0.3) are employed to build 40 QSRR models. The statistical outcomes of each target function are compared with each other. The better predictive potential is obtained for the models generated by the combination of the index of ideality of correlation (IIC) and correlation intensity index (CII). The statistical quality of the established QSPR model of split 5 calculated by TF3 is better than that of the other models, so it is considered to be the best model (Rvalidation2 = 0.8162, IIC = 0.6554, CII = 0.8787, CCC = 0.8734, Q2 = 0.7778 and RMSE = 0.2213). The promoters of increase and decrease of rate constants are also extracted from three splits 4, 5 and 8. [ABSTRACT FROM AUTHOR]

A new beryllium-free deep-UV transparent NLO crystal Li(H2O)2Sc(SO4)2 features a two-dimensional [Sc(SO4)2] framework consisting of twisted [Sc3S4O9] units decorated by [LiO2(H2O)2] groups into a unique layer. Remarkably, Li(H2O)2Sc(SO4)2 exhibits a phase-matching SHG response of 0.7 × KDP and a deep-UV cutoff edge below 190 nm. [ABSTRACT FROM AUTHOR]

Agar is a polysaccharide mixture extracted from red algae. Agar has been widely used in food, medicine and biochemistry, because of its gelling properties and stability. However, sulfate groups in the structure of agar weaken the gel strength of agar; hence, sulfate removal is necessary to improve the agar quality. The commonly used alkali desulfation greatly pollutes the environment, and enzymatic desulfation is costly due to the need for a large amount of the enzyme. In this work, microorganisms were for the first time used for agar desulfation, taking advantage of the sulfur demand of microorganisms themselves. This allows the removal of agar sulfate groups to be eco-friendly and effective. Firstly, microorganism strains were screened with agar as the sole sulfur source. Then 4 microorganism-based agar desulfation techniques, sulfate removal from agar liquid at 60 °C, from an solid agar plate at 37 °C, from freshly-prepared agar slices in liquid medium, and from agar strips without pretreatment (ASWP) in liquid medium, were established and compared. Finally, by using Priestia megaterium WMX, the sulfate removal rate from ASWP reached 74.67%, and the gel strength increased by 187%, reaching 1173 g cm−2. Therefore, the agar quality was greatly improved by sulfate removal with microorganisms. The microorganism-based agar desulfation technique established in this work is easy-to-perform, cost effective, and an eco-friendly way to improve agar quality and has the potential to be applied on the industrial scale. [ABSTRACT FROM AUTHOR]

The precursor compound plays a crucial role in the development of low-cost chalcogenide thin-film solar cells via a solution approach. In this work, we report on the synthesis of a new complex [Cu((NH2)2CS)3]2SO4·H2O through a simple redox reaction between inexpensive Cu(CH3COO)2·H2O and thiourea (TU) in water. Using this complex as a copper source, a stable dimethylformamide solution was made and copper indium sulfoselenide CuIn(S,Se)2 thin film solar cells with a high efficiency of 12.2% have been demonstrated. [ABSTRACT FROM AUTHOR]

Biodesulfurization is a biotechnological process that employs microorganisms as biocatalysts to remove sulfur from fuels usually at mesophilic conditions, targeting recalcitrant organosulfur compounds without affecting their hydrocarbon structure. One of the bottlenecks hindering its large-scale application is the inhibition of biodesulfurization activity by easily metabolized sulfur compounds, such as sulfates, even at residual concentrations. This increases production costs by requiring high-purity sulfur-free nutrients or complex induction steps to prevent/revert inhibition. The objective of this work was to bypass this limitation and demonstrate that it is possible to produce biocatalysts with biodesulfurization activity using sulfate as the only sulfur source, without employing inducers or genetic manipulation, simply by adjusting the sulfur : carbon ratio in continuous culture. With this goal, the bacterium Gordonia alkanivorans strain 1B was cultivated in a chemostat with a medium containing 10 g L−1 of fructose as the carbon source and different sulfate concentrations (12–50 mg per L SO42−) using Na2SO4. Then the bacteria were employed as biocatalysts in biodesulfurization assays with a recalcitrant organosulfur compound (dibenzothiophene). Under these conditions it was observed that 2.2 mgsulfate gfructose−1 ensured a biodesulfurization activity of 6.1 μmol gDCW−1 h−1, 15% greater than previously reported for this strain with an inducer, without limiting biocatalyst production. This novel procedure was further applied to another biocatalyst, Rhodococcus erythropolis strain D1, validating its wide applicability to other desulfurizing microorganisms. Overall, these results indicate a previously unknown regulation mechanism dependent on relative sulfur concentration, which influences cellular responses and regulates biodesulfurization activity, allowing the use of easily metabolized sulfur sources to produce cost-effective biocatalysts for biodesulfurization. [ABSTRACT FROM AUTHOR]

By the introduction of trivalent rare-earth metal-centered polyhedra [LnO6F4] (Ln = La, Gd) into alkali metal sulfates, two novel sulfate fluorides, NaLn2(SO4)2F3 (Ln = La, Gd), were successfully synthesized via a high-temperature solution method in sealed quartz tubes. The two compounds are isomorphic and feature a structure composed of [LnO6F4] (Ln = La, Gd) polyhedra, [NaO4F3] polyhedra, and [SO4] groups. The UV-vis-NIR diffuse reflection spectra, infrared spectra, and thermal stability are also presented. Meanwhile, theoretical calculations reveal that NaLa2(SO4)2F3 has a moderate birefringence (0.041 at 1064 nm) which is significantly improved compared with Na2SO4. And the enhancement of birefringence can be ascribed to the introduction of rare-earth metal-centered polyhedra by a real space atom-cutting method. This work shows that the introduction of trivalent rare-earth metal-centered polyhedra is one of the effective strategies for bolstering the birefringence performance of non-π-conjugated sulfate systems. [ABSTRACT FROM AUTHOR]

Ce3+–Tb3+–Eu3+ triply doped Ba3KPO4(SO4)2 phosphors were synthesized and extensively studied. The luminescence properties, concentration effect and energy transfer (ET) mechanism of phosphors were studied in detail using the photoluminescence spectra and decay curves. The luminescent color of Ce3+–Tb3+–Eu3+ triply doped Ba3KPO4(SO4)2 phosphors can be tuned by adjusting the ET between different dopants. Spectroscopy studies demonstrate that Tb3+ acts as a bridge via Ce3+–Tb3+–Eu3+ ET in Ba3KPO4(SO4)2. The combined effects of energy-transfer on the emission color of Ce3+–Tb3+–Eu3+ show that the newly synthesized Ba3KPO4(SO4)2:Ce3+/Tb3+/Eu3+ phosphors can be used as a potential color converter with a large color gamut. [ABSTRACT FROM AUTHOR]

Herein we report the design and synthesis of a terphen[n]arene derivative functionalised with sulfate acid ester groups. This water-soluble terphen[3]arene host effectively encapsulates a multitude of neuromuscular blocking agents (NMBAs) with high affinity, showing great potential as a NMBAs reversal agent in pharmaceutical research. [ABSTRACT FROM AUTHOR]

By a simple hydrothermal method, a phase boundary between α- and β-Ni(OH)2 can be obtained. The Fenton-like performance of α@β-Ni(OH)2 is 1.56 times higher than that of single β-Ni(OH). α@β-Ni(OH)2 displays superior stability compared to α-Ni(OH)2, β-Ni(OH)2, and amorphous Ni(OH)2, which makes significant contributions to developing advanced catalysts in diverse fields. [ABSTRACT FROM AUTHOR]

In this paper, the effects of sulfuric acid treatment of a ZrO2 support (ZrO2-S) on the Ca resistance of CeO2 catalysts were investigated. The results showed that the CeO2/ZrO2-S catalyst exhibited much better SCR activity and Ca resistance compared with the CeO2/ZrO2 catalyst. To further reveal the Ca resistance mechanism, BET, XRD, Raman, XPS, H2-TPR, NH3-TPD and in situ DRIFTS were used to characterize the changes in structure and properties of the CeO2/ZrO2 and CeO2/ZrO2-S catalysts before and after the Ca deactivation tests. The Ca poisoning of the CeO2/ZrO2 catalysts was mainly due to the decrease in specific surface area and surface acidity, the loss of reducibility and the enhanced stabilization of adsorbed nitrate/nitrite species. The treatment of ZrO2 with sulfate acid led to an increased specific surface area and highly-dispersed Ce species at the catalyst surface. It was also beneficial to inhibiting the transformation of ZrO2 from the tetragonal to the monoclinic phase. Moreover, it also enhanced the redox properties, Ce3+ species ratio, total surface acidity (especially Brønsted acid sites), and adsorption of NH3 species. The SCR reactions via both Langmuir–Hinshelwood (L–H) and Eley–Rideal (E–R) mechanisms could proceed well even after the CeO2/ZrO2-S catalysts were subjected to Ca poisoning. [ABSTRACT FROM AUTHOR]

In this paper, the effects of sulfuric acid treatment of a ZrO2 support (ZrO2-S) on the Ca resistance of CeO2 catalysts were investigated. The results showed that the CeO2/ZrO2-S catalyst exhibited much better SCR activity and Ca resistance compared with the CeO2/ZrO2 catalyst. To further reveal the Ca resistance mechanism, BET, XRD, Raman, XPS, H2-TPR, NH3-TPD and in situ DRIFTS were used to characterize the changes in structure and properties of the CeO2/ZrO2 and CeO2/ZrO2-S catalysts before and after the Ca deactivation tests. The Ca poisoning of the CeO2/ZrO2 catalysts was mainly due to the decrease in specific surface area and surface acidity, the loss of reducibility and the enhanced stabilization of adsorbed nitrate/nitrite species. The treatment of ZrO2 with sulfate acid led to an increased specific surface area and highly-dispersed Ce species at the catalyst surface. It was also beneficial to inhibiting the transformation of ZrO2 from the tetragonal to the monoclinic phase. Moreover, it also enhanced the redox properties, Ce3+ species ratio, total surface acidity (especially Brønsted acid sites), and adsorption of NH3 species. The SCR reactions via both Langmuir–Hinshelwood (L–H) and Eley–Rideal (E–R) mechanisms could proceed well even after the CeO2/ZrO2-S catalysts were subjected to Ca poisoning. [ABSTRACT FROM AUTHOR]

1,1′-Bis[squaramido]ferrocenes (FcSq2) are introduced as electrochemically active scaffolds for sulfate recognition. FcSq2 display high sulfate-binding affinity and selectivity in aqueous DMSO mixtures. Among tested anions, sulfate elicits a unique electrochemical response in FcSq2, enabling selective detection. [ABSTRACT FROM AUTHOR]

A new family of hybrid organic–inorganic layered materials based on nickel sulfates was synthesized using a simple, solvent-free synthesis approach using 1,2-phenylenediamine (OPD), 1,3-phenylenediamine (MPD), and 1,4-phenylenediamine (PPD) as organic templates and ligands. Diamines act as structure-directing agents to obtain 1D [Ni(OPD)2SO4] (1), 2D [Ni(MPD)2SO4] (2) and 3D [Ni(PPD)SO4] (3) frameworks. The crystal structures of 1–3 were determined using data from X-ray powder diffraction (XRPD) measurements and represent I2/a, Cc, and Cmcm space groups, respectively. The compounds display different dimensionalities of the frameworks; however, the magnetic studies reveal transitions to 3D magnetic long-range ordered phases in all three cases below 23 K (1), 25 K (2) and 25 K (3). The observed ordering in all compounds is a consequence of significant interchain (1) and intralayer (2 and 3) interactions which lead to considerable spin–spin correlations, which are strong enough to couple the adjacent layers. In addition, in all three compounds, there is a competition between ferromagnetic and antiferromagnetic interactions in which the latter ones successively get stronger with the substitution of dipolar couplings by superexchange ones. [ABSTRACT FROM AUTHOR]

We report the first example of a perovskite sulfate [Na3(H2O)]Fe(SO4)3. Further structure modulation, by dimensional reduction or ligand extension, has resulted in two related layered perovskite-like compounds Na6Fe(SO4)4 and Na12Fe3(SO4)6F8. Taken together, these results open up a more general strategy for the future design of more complex perovskite-related materials. [ABSTRACT FROM AUTHOR]

Our theoretical treatment of electronic structures in coordination complexes often rests on assumptions of symmetry. Experiments rarely provide fully symmetric systems to study. In solutions, fluctuations in solvation, variations in conformations, and even changes in constitution occur and complicate the picture. In crystals, lattice distortion, energy transfer, and phonon quenching play a role, but we are able to identify distinct symmetries. Yet the question remains: How is the real symmetry in a crystal compared to ideal symmetries? [ABSTRACT FROM AUTHOR]

We recently presented a new method that allows for a direct structural comparison of coordination complexes. The main difference from other methods is that our AlignIt approach uses common scaling and orientation of the complexes when computing the symmetry deviation, σideal, values. Here, six apparently isostructural lanthanide(III) sulfates K6[(Ln)2(SO4)6]/K5Na[(Ln)2(SO4)6] with ten-coordinated lanthanide(III) sites (Ln(O)10) were prepared, and single-crystal structures were determined and compared using the symmetry deviation (σideal) values. The six structures were shown to fall into two groups: Pr(III) and Eu(III) are identical (σideal = 0.04) bar in size. With a maximum σideal of 0.07, the same was found to be true for La(III), Ce(III), Nd(III), Sm(III) structures. The two groups are shown to be significantly different (σideal > 2.7), yet the coordination geometries of all six are best described as bicapped square antiprisms (σideal = 1.15–1.68). The structures differ in more than symmetry as the smaller lanthanides are shown to crystallize with one sodium and five potassium ions, while the larger lanthanides crystallize with six potassium ions. This does not change the structure and we postulate that the structural variation is due to delicate size matching between alkali and lanthanide ions. For the first six lanthanides, this structure is very robust, which is confirmed as seven doped systems readily crystallized. These doped systems were prepared in order to use europium(III) luminescence as a structural probe. Unsurprisingly, only the doped Eu–La and Eu–Ce systems were found to be luminescent. Between these two and all the europium(III) systems, the intricate structural differences were shown to be enough to change both crystal field splitting and luminescence lifetime. We conclude that even in simple dilution experiments, where luminescent lanthanide(III) ions are introduced in 'innocent' hosts materials, the structure can act as a modulator for the observed properties. [ABSTRACT FROM AUTHOR]

Inspired by the working principle of natural spiderweb and long-persistence phosphors, we have synthesized a spiderweb-like nanocomposite in which CoS quantum dots are confined in N-doped carbon frameworks/carbon nanotubes (CNTs). The intimate combination of three-dimensional conductive networks of CoS/CNTs with abundant active sites allows effective capture of sulfate radicals via both physical confinement and chemical bonding and accelerates the redox kinetics significantly. Furthermore, in virtue of the light storing and luminescence behaviors of long-persistence phosphors, the all-weather CoS/CNTs produced can realize an optimum degradation efficiency of 64% under dark conditions. Overall, this work reveals a significant step forward for building a desirable all-weather catalyst with abundant active sites for potential use in degradation under dark conditions. [ABSTRACT FROM AUTHOR]

Atmospheric sulfate is widespread in the Earth system and has climate and environmental impacts. The oxygen isotope mass independent fractionation signal (i.e., Δ17O = δ17O − 0.52 × δ18O) of sulfate is a very useful metric to probe the specific formation pathways of atmospheric sulfate, and has implications for atmospheric oxidation chemistry. However, currently there is no O-17 enriched sulfate international reference material available for Δ17O(SO42−) analysis and calibration. In this study, we introduced a new and cost-effective method that uses purified ozone reacting with sodium sulfite solution to produce O-17 enriched sulfate. In this way, we made three sodium sulfate materials enriched in O-17 with different magnitudes, and termed them Sulf-A, Sulf-B and Sulf-C. The Δ17O values of these materials were quantified using the pyrolysis method in quartz and platinum capsules. The pyrolysis system was tested by analyzing the nitrate international reference material USGS35 with a measured Δ17O value of (21.72 ± 0.15)‰ that is consistent with the accepted value. For the sulfate materials, we obtained average Δ17O values of (0.64 ± 0.06)‰, (2.09 ± 0.14)‰ and (6.48 ± 0.18)‰ (1σ) for Sulf-A, Sulf-B and Sulf-C, respectively, when measured in platinum capsules. And these were adopted as their accepted values. Although additional measurements may be necessary to verify the accuracy of the Δ17O values of Sulf-A, Sulf-B and Sulf-C, they can serve as working standards for routine Δ17O(SO42−) analysis of samples of interest to improve data consistency. [ABSTRACT FROM AUTHOR]

Two polymorphs of the borosulfate Cu[B2(SO4)4] can be selectively prepared by solvothermal syntheses. The crystal structures of inosilicate-analogous α-Cu[B2(SO4)4] (P1¯, no. 2, a = 5.2636(2), b = 7.1449(2), c = 7.9352(2) Å, α = 73.698(2)°, β = 70.737(2)°, γ = 86.677(2)°, 65 parameters, RBragg = 0.0052) and the new phyllosilicate-analogous polymorph β-Cu[B2(SO4)4] (P21/n, no. 14, a = 7.712(3), b = 8.149(3), c = 9.092(3) Å, β = 111.22(1)°, 3829 independent reflections, 106 parameters, wR2 = 0.054) are discussed. Further, the optical, magnetic and thermal properties of both polymorphs are investigated with focus on the role of the Cu2+ cation and its Jahn–Teller effect. The findings are confirmed by DFT calculations yielding insights in the stability of the synthesised polymorphs as well as a predicted γ-modification. Additionally, the crystal structures of two polymorphs of copper hydrogensulfate Cu(HSO4)2-I (P21/n, no. 14, a = 4.7530(2), b = 8.5325(4), c = 7.3719(3) Å, β = 100.063(1)°, 1063 independent reflections, 55 parameters, wR2 = 0.052) and Cu(HSO4)2-II (P1¯, no. 2, a = 4.79.88(8), b = 7.857(1), c = 8.057(1) Å, α = 77.86(1)°, β = 87.02(1)°, γ = 89.82(1)°, 1044 independent reflections, 109 parameters, wR2 = 0.132) as well as that of Cu[S2O7] (C2/c, no. 15, a = 6.6341(4), b = 8.7302(5), c = 9.0555(8) Å, β = 104.763(3)°, 1117 independent reflections, 48 parameters, wR2 = 0.049) are presented and the cyclosilicate-analogous borosulfate Cu[B(SO4)2(HSO4)] is fully characterised with respect to its optical and thermal properties. [ABSTRACT FROM AUTHOR]

Two polymorphs of the borosulfate Cu[B2(SO4)4] can be selectively prepared by solvothermal syntheses. The crystal structures of inosilicate-analogous α-Cu[B2(SO4)4] (P1¯, no. 2, a = 5.2636(2), b = 7.1449(2), c = 7.9352(2) Å, α = 73.698(2)°, β = 70.737(2)°, γ = 86.677(2)°, 65 parameters, RBragg = 0.0052) and the new phyllosilicate-analogous polymorph β-Cu[B2(SO4)4] (P21/n, no. 14, a = 7.712(3), b = 8.149(3), c = 9.092(3) Å, β = 111.22(1)°, 3829 independent reflections, 106 parameters, wR2 = 0.054) are discussed. Further, the optical, magnetic and thermal properties of both polymorphs are investigated with focus on the role of the Cu2+ cation and its Jahn–Teller effect. The findings are confirmed by DFT calculations yielding insights in the stability of the synthesised polymorphs as well as a predicted γ-modification. Additionally, the crystal structures of two polymorphs of copper hydrogensulfate Cu(HSO4)2-I (P21/n, no. 14, a = 4.7530(2), b = 8.5325(4), c = 7.3719(3) Å, β = 100.063(1)°, 1063 independent reflections, 55 parameters, wR2 = 0.052) and Cu(HSO4)2-II (P1¯, no. 2, a = 4.79.88(8), b = 7.857(1), c = 8.057(1) Å, α = 77.86(1)°, β = 87.02(1)°, γ = 89.82(1)°, 1044 independent reflections, 109 parameters, wR2 = 0.132) as well as that of Cu[S2O7] (C2/c, no. 15, a = 6.6341(4), b = 8.7302(5), c = 9.0555(8) Å, β = 104.763(3)°, 1117 independent reflections, 48 parameters, wR2 = 0.049) are presented and the cyclosilicate-analogous borosulfate Cu[B(SO4)2(HSO4)] is fully characterised with respect to its optical and thermal properties. [ABSTRACT FROM AUTHOR]

A metal–organic framework (MOF) built from a combination of metal cations, neutral azole ligands and sulphate anions, [Cu2(DHBDI)3(SO4)2]n (1, DHBDI = 1H,5H-benzo[1,2-d:4,5-d′]diimidazole), was synthesized. MOF 1 exhibits good chemical stability in acids, bases and boiling water while showing high hydrophilicity. Meanwhile, MOF 1 exhibits a proton conductivity of 1.14 × 10−3 S cm−1 at 90 °C and 98% RH, among the best for MOF materials with uncoordinated N sites. Temperature-dependent conductivity measurements suggest a vehicle mechanism (Ea = 0.64 eV) for proton transport. [ABSTRACT FROM AUTHOR]

A series of new photoresponsive macrocyclic anion receptors were synthesized via integration of an azobenzene unit and multiple anion binding sites. They exhibited highly selective binding to dianionic sulfate over other tested anions and the reversible release of sulfate could be triggered by visible light as inferred from mass spectroscopy, crystallographical analysis, NMR spectroscopy, and theoretical calculations. [ABSTRACT FROM AUTHOR]

Two bismuth iodate sulfates crystallizing in the monoclinic space group P21/c, namely, Bi(IO3)(SO4) and CdBi(IO3)(SO4)2, were synthesized via solvothermal reactions. Bi(IO3)(SO4) features 2D [Bi(SO4)]+ layers, which are further linked by the IO3− groups to form a 3D network. CdBi(IO3)(SO4)2 exhibits 1D [IO3]− chains built from IO43− groups via corner-sharing and is the first example of a polyiodate sulfate as far as we know. These [IO3]− chains are interconnected by Bi3+ cations into [Bi(IO3)]2+ layers parallel to the bc plane, whereas the neighbouring Cd2+ cations are interconnected by bridging SO42− anions into [Cd(SO4)2]2− layers, also parallel to the bc plane. These cationic and anionic 2D layers are held together through Bi–O–S bridges into a complicated 3D framework. Bi(IO3)(SO4) and CdBi(IO3)(SO4)2 show wide band gaps of 3.91 and 4.03 eV and large birefringence values of 0.087 and 0.100 at 1064 nm, respectively. Our work indicates that the introduction of iodate group and lone pair cations, such as Bi3+, into metal sulfates can greatly enhance their birefringent properties. [ABSTRACT FROM AUTHOR]

We report the crystal structures of two tin(IV) sulfate polymorphs Sn(SO4)2-I (P21/c (no. 14), a = 504.34(3), b = 1065.43(6), c = 1065.47(6) pm, β = 91.991(2)°, 4617 independent reflections, 104 refined parameters, wR2 = 0.096) and Sn(SO4)2-II (P21/n (no. 14), a = 753.90(3), b = 802.39(3), c = 914.47(3) pm, β = 92.496(2)°, 3970 independent reflections, 101 refined parameters, wR2 = 0.033). Moreover, the first heterovalent tin sulfate Sn2(SO4)3 is reported which adopts space group P1¯ (no. 2) (a = 483.78(9), b = 809.9(2), c = 1210.7(2) pm, α = 89.007(7)°, β = 86.381(7)°, γ = 73.344(7)°, 1602 independent reflections, 152 refined parameters, wR2 = 0.059). Finally, SnSO4 – the only tin sulfate with known crystal structure – was revised and information complemented. The optical and thermal properties of all tin sulfates are investigated by FTIR, UV-vis, luminescence and 119Sn Mössbauer spectroscopy as well as thermogravimetry and compared. [ABSTRACT FROM AUTHOR]

We have demonstrated that cisplatin (CP), an anticancer drug, showed a preference for binding the sulfated-L-iduronic acid (S-L-IdoA) unit over the sulfated-D-glucuronic acid unit of heparan sulfate. The multivalency of S-L-IdoA, such as in the proteoglycan mimic, resulted in distinct modes of cell-surface engineering in normal and cancer cells, with these disparities having a significant impact on CP-mediated toxicity.

The extracellular matrix (ECM) presents a framework for various biological cues and regulates homeostasis during both developing and mature stages of tissues. During development of cartilage, the ECM plays a critical role in endowing both biophysical and biochemical cues to the progenitor cells. Hence, designing microenvironments that recapitulate these biological cues as provided by the ECM during development may facilitate the engineering of cartilage tissue. In the present study, we fabricated an injectable interpenetrating hydrogel (IPN) system which serves as an artificial ECM and provides chondro-inductive niches for the differentiation of stem cells to chondrocytes. The hydrogel was designed to replicate the gradual stiffening (as a biophysical cue) and the presentation of growth factors (as a biochemical cue) as provided by the natural ECM of the tissue, thus exemplifying a biomimetic approach. This dynamic stiffening was achieved by incorporating silk fibroin, while the growth factor presentation was accomplished using sulfated-carboxymethyl cellulose. Silk fibroin and sulfated-carboxymethyl cellulose (s-CMC) were combined with tyraminated-carboxymethyl cellulose (t-CMC) and crosslinked using HRP/H 2 O 2 to fabricate s-CMC/t-CMC/silk IPN hydrogels. Initially, the fabricated hydrogel imparted a soft microenvironment to promote chondrogenic differentiation, and with time it gradually stiffened to offer mechanical support to the joint. Additionally, the presence of s-CMC conferred the hydrogel with the property of sequestering cationic growth factors such as TGF-β and allowing their prolonged presentation to the cells. More importantly, TGF-β loaded in the developed hydrogel system remained active and induced chondrogenic differentiation of stem cells, resulting in the deposition of cartilage ECM components which was comparable to the hydrogels that were treated with TGF-β provided through media. Overall, the developed hydrogel system acts as a reservoir of the necessary biological cues for cartilage regeneration and simultaneously provides mechanical support for load-bearing tissues such as cartilage.

The gut health-promoting properties of saponin-rich Polygonatum cyrtonema Hua (FP) fermented with Lactobacillus plantarum P9 were explored in a dextran sulfate sodium (DSS)-induced colitis mouse model. FP supplementation effectively inhibited DSS-induced physiological alteration and impaired immune responses by reducing the disease activity index (DAI) score and restoring the T helper (Th) 1/Th2 and regulatory T (Treg)/Th17 ratios. In addition, FP supplementation protected the gut barrier function against DSS-induced damage via upregulation of zonula occludens (ZO)-1 and occludin and downregulation of pro-inflammatory cytokines, including interleukin (IL)-1β, tumor necrosis factor-α (TNF-α), IL-18, and the granulocyte-macrophage colony-stimulating factor (GM-CSF). This study further elucidated the potential mechanisms underlying the FP-mediated suppression of the plasticity of type 3 innate lymphoid cells (ILC3) and subsequent macrophage polarization. Therefore, the FP supplementation effectively restored mucosal immune homeostasis and enhanced gut integrity. In addition, it suppressed the growth of Escherichia-Shigella and Enterococcus and promoted the enrichment of probiotics and short-chain fatty acid-producing microbes, such as Romboutsia , Faecalibaculum , and Blautia . In conclusion, P. cyrtonema Hua fermented with L. plantarum P9 might be a promising dietary intervention to improve gut health by sustaining overall gut homeostasis and related gut integrity.

Biomembranes are a key component of all living systems. Most research on membranes is restricted to ambient physiological conditions. However, the influence of extreme conditions, such as the deep subsurface on Earth or extraterrestrial environments, is less well understood. The deep subsurface of Mars is thought to harbour high concentrations of chaotropic salts in brines, yet we know little about how these conditions would influence the habitability of such environments. Here, we investigated the combined effects of high concentrations of Mars-relevant salts, including sodium and magnesium perchlorate and sulphate, and high hydrostatic pressure on the stability, structure, and function of a bacterial model membrane. To this end, several biophysical techniques have been employed, including calorimetry, fluorescence and CD spectroscopy, confocal microscopy, and small-angle X-ray scattering. We demonstrate that sulphate and perchlorate salts affect the properties of the membrane differently, depending on the counterion present (Na + vs. Mg 2+ ). We found that the perchlorates, which are believed to be abundant salts in the Martian environment, induce a more hydrated and less ordered membrane, strongly favouring the physiologically relevant fluid-like phase of the membrane even under high-pressure stress. Moreover, we show that the activity of the phospholipase A2 is strongly modulated by both high pressure and salt. Compellingly, in the presence of the chaotropic perchlorate, the enzymatic reaction proceeded at a reasonable rate even in the presence of condensing Mg 2+ and at high pressure, suggesting that bacterial membranes could still persist when challenged to function in such a highly stressed Martian environment.

N -Acetylgalactosamine-6-sulfatase (GALNS) is an enzyme whose deficiency is related to the lysosomal storage disease Morquio A. For the development of effective therapeutic approaches against this disease, the design of suitable enzyme enhancers ( i.e. pharmacological chaperones) is fundamental. The natural substrates of GALNS are the glycosaminoglycans keratan sulfate and chondroitin 6-sulfate, which mainly display repeating units of sulfated carbohydrates. With a biomimetic approach, gold nanoparticles (AuNPs) decorated with simple monosaccharides, sulfated ligands (homoligand AuNPs), or both monosaccharides and sulfated ligands (mixed-ligand AuNPs) were designed here as multivalent inhibitors of GALNS. Among the homoligand AuNPs, the most effective inhibitors of GALNS activity are the β-D-galactoside-coated AuNPs. In the case of mixed-ligand AuNPs, β-D-galactosides/sulfated ligands do not show better inhibition than the β-D-galactoside-coated AuNPs. However, a synergistic effect is observed for α-D-mannosides in a mixed-ligand coating with sulfated ligands that reduced IC 50 by one order of magnitude with respect to the homoligand α-D-mannoside-coated AuNPs. SAXS experiments corroborated the association of GALNS with β-D-galactoside AuNPs. These AuNPs are able to restore the enzyme activity by almost 2-fold after thermal denaturation, indicating a potential chaperoning activity towards GALNS. This information could be exploited for future development of nanomedicines for Morquio A. The recent implications of GALNS in cancer and neuropathic pain make these kinds of multivalent bionanomaterials of great interest towards multiple therapies.

The green tea polyphenol, (-)-epigallocatechin-3-gallate (EGCG), has been studied for its potential positive health effects, but human and animal model studies have reported potential toxicity at high oral bolus doses. This study used liquid chromatography-mass spectrometry-based metabolomics to compare the urinary EGCG metabolite profile after administration of a single non-toxic (100 mg kg -1 ) or toxic (750 mg kg -1 ) oral bolus dose to male C57BL6/J mice to better understand how EGCG metabolism varies with dose. EGCG metabolites, including methyl, glucuronide, sulfate, and glucoside conjugates, were tentatively identified based on their mass to charge ( m / z ) ratio and fragment ion patterns. Partial least squares discriminant analysis (PLS-DA) results showed clear separation of the urine metabolite profiles between treatment groups. The most differentiating metabolites in the negative and positive ion modes were provisionally identified as di-glucuronidated EGCG quinone and di-glucuronidated EGCG, respectively. The presence of EGCG oxidation products at toxic dose is consistent with studies showing that EGCG toxicity is associated with oxidative stress. Relative amounts of methylated metabolites increased with dose to a lesser extent than glucuronide and sulfate metabolites, indicating that methylation is more prominent at low doses, whereas glucuronidation and sulfation may be more important at higher doses. One limitation of the current work is that the lack of commercially-available EGCG metabolite standards prevented absolute metabolite quantification and identification. Despite this limitation, these findings provide a basis for better understanding the dose-dependent changes in EGCG metabolism and advance studies on how these differences may contribute to the toxicity of high doses of EGCG.

Objective : The first objective is to study the synergistic inhibition of calcium oxalate (CaOx) formation by Laminarin polysaccharides (DLP and SDLP, before and after sulfation) and potassium citrate (K 3 cit) and determine the synergistic protection of renal epithelial cells (HK-2 cells) caused by CaOx crystal damage. The second objective is to explore new ways to prevent and treat kidney stones. Methods : The CaOx crystals regulated by five additives (K 3 cit group, DLP group, SDLP group, DLP-K 3 cit synergistic group and SDLP-K 3 cit synergistic group) were characterized by FT-IR, XRD, SEM, zeta potential, ICP, and TGA. The protective effect of each additive group on HK-2 cells damaged by nano-calcium oxalate monohydrate (nano-COM) was compared by detecting cell viability, the cell reactive oxygen species level, the cell survival rate, and mitochondrial membrane potential. Results : When DLP or SDLP acted synergically with K 3 cit, the synergistic group induced the same amount of COD at a lower concentration or more COD formation at the same concentration, highlighting the synergistic enhancement effect of 1 + 1 > 2. At 0.3 g L -1 , the COD contents induced by DLP, SDLP, K 3 cit, DLP-K 3 cit, and SDLP-K 3 cit synergistic groups were 20.3%, 75.8%, 75.4%, 87.3%, and 100%, respectively. The synergistic group increased the concentration of soluble Ca 2+ ions in the supernatant, increased the absolute value of the zeta potential on the surface of CaOx crystals, and inhibited the aggregation among the crystals. TGA and DTG analyses established the adsorption of polysaccharides in the crystals. Cell experiments showed the ability of the synergistic group to significantly inhibit the damage of nano-COM crystals on HK-2 cells, reduce the level of reactive oxygen species and mortality, and improve cell viability and the mitochondrial membrane potential. Conclusions : The synergistic group can more effectively induce COD formation and cell protection than the standalone polysaccharide group or K 3 cit group. The synergistic groups, especially SDLP-K 3 cit, may be a potential drug for inhibiting the formation of CaOx kidney stones.

Two novel compounds isolated from an amber sample from the Santonian of Piolenc (Vaucluse, SE France) were identified using nuclear magnetic resonance and high-resolution mass spectrometry as sulfurized analogues of diterpenic acids from the isopimaric series originating from ancient conifers possibly related to the Cupressaceae family. These two compounds are members of a diterpenoid series corresponding to early diagenetic transformation products of resin diterpenoids. They were likely formed once plant resin comes into contact with reduced sulfur species originating from bacterial sulfate reduction occurring in anaerobic settings such as mangroves or marshes. They represent the first evidence of sulfurization processes affecting plant resin prior to diagenetic transformation into amber. Given their mode of formation, these compounds may be used as indicators of sulfate-reducing processes in past depositional environments.

Osteoporosis is a growing public health concern worldwide. To avoid extra surgeries, developing biodegradable bone cement is critical for the treatment of osteoporosis. Herein, we designed calcium phosphate/calcium sulfate cement reinforced with sodium carboxymethyl cellulose (CMC/OPC). It presents an appropriate physicochemical performance for clinical handling. Meanwhile, CMC/OPC bone cement promotes osteogenic differentiation in vitro . Results of the immune response in vitro and in vivo confirmed that increasing the cellulose content triggered macrophage switching into the M2 phenotype and CMC/OPC exhibited significant anti-inflammation. Furthermore, in vitro and in vivo degradation demonstrated that cellulose tailors the degradation rate of composite bone cement, which achieved a linear degradation process and could degrade by more than 90% for 12 weeks. In summary, the composite bone cement CMC/OPC is a promising candidate for bone repair applications.

Polysaccharides are a major functional component of seaweeds with various biological activities. Porphyra haitanensis is usually harvested in different growth periods, but how the harvest periods influence the Porphyra haitanensis polysaccharide (PHP) activity is unclear. This work aimed to evaluate the anti-allergic activity of PHP from different harvest periods and investigate the potential structure-activity relationship. The water-soluble polysaccharide of P. haitanensis from three different harvest periods was purified and administered to an ovalbumin-sensitized food allergy mouse model. Results showed that PHPs significantly alleviated the allergic symptoms and reduced the production of histamine and allergen-specific IgE. Further experiments elucidated that PHPs suppressed the allergic activity of intestinal epithelial cells, dendritic cells, and Th2 cells and downregulated the proportion of Th2 cells. Noticeably, the molecular weight and sulfate content gradually decreased as the harvest period was delayed; simultaneously, the anti-allergic activity gradually increased, implying a relationship between the harvest period, structure, and anti-allergic activity of PHPs. This work elucidated the anti-allergic activity of PHPs from different harvest periods, facilitated the deep-processing and efficient application of Porphyra haitanensis , and shed light on the development of novel anti-allergic functional foods.

Milt is an underutilized fish processing by-product containing valuable nutrients for human health. Here, a gastrointestinal hydrolysate of degreased yellowtail ( Seriola quinqueradiata ) milt contained 70.6% arginine-rich protein, 20% nucleic acids, 7.1% minerals and 2.3% carbohydrates. Yellowtail milt hydrolysates (YMH) effectively attenuated the H 2 O 2 -induced burst of intracellular reactive oxygen species, plasma membrane impairment, loss of cell viability, interleukin 8 production and the expression of claudin-4 and occludin in Caco-2 cells with its protein fraction playing a greater antioxidant role than its nucleic acid fraction. YMH also significantly counteracted the tumor necrosis factor α- and interleukin 1β-stimulated interleukin 8 production and cyclooxygenase-2 and inducible nitric oxide synthase expression in Caco-2 cells and inhibited the production of nitric oxide and proinflammatory mediators in lipopolysaccharide-stimulated RAW 264.7 cells depending on its protein fraction, rather than its nucleic acid fraction. YMH and a positive drug 5-aminosalicylic acid were intragastrically administered to C57BL/6 mice daily for 7 days during and after 4-day dextran sodium sulphate exposure. Based on clinical signs, colon histopathology and biochemical analysis of colonic tight junction proteins, mucus compositions and goblet cells, YMH ameliorated mouse colitis symptoms and intestinal epithelial barrier dysfunction more effectively than 5-aminosalicylic acid. According to myeloperoxidase activity, proinflammatory cytokines and NF-κB, YMH and 5-aminosalicylic acid exerted equivalent inhibitory effects on colonic and systemic inflammation. Overall, YMH have considerable antioxidant and anti-inflammatory efficacies to maintain gut health.

The speciation of both redox reactive and volatile selenium (Se) compounds, barely reported in pristine aquatic environments, has never been investigated in remote alpine lakes, considered as sensitive ecosystems to detect the effect of global change. This work presents an integrated investigation on Se distribution and speciation conducted in 20 high altitude pristine lakes from the central-western Pyrenees. Five seasonal sampling campaigns were carried out after snowmelt (June/July) and in early fall (October) for the period 2017-2019. Concentrations of total dissolved Se (TDSe) ranged from 7 to 78 ng L -1 , with selenate being ubiquitously observed in most cases (median of 61% of TDSe). Selenite was only occasionally detected up to 4 ng L -1 , therefore a fraction of TDSe was presumably in the forms of elemental Se(0) and/or selenides. Depth profiles obtained in different lakes showed the occurrence of such Se(-II, 0) pools in bottom hypoxic to anoxic waters. The production of volatile Se compounds presented a low median total concentration (TVSe) of 33 pg L -1 (range 3-120 pg L -1 ), mainly in the form of dimethylselenide in subsurface samples (median of 82% of TVSe). The Se concentration in lake waters was significantly correlated with the sulphate concentration ( ρ = 0.93, p < 0.0001), demonstrating that it is influenced by erosion and dissolution of Se and S-enriched parent bedrocks. In addition, for Se depleted alpine lake-bedrock systems, long-range transport and wet atmospheric depositions represent a major source of Se for lake waters.

Arsenic (As) and sulfate pollution are often found co-occurring as a result of smelting metal ores. Previous studies showed that sulfate reducing microbes (SRMs) can use As(V) as a terminal electron acceptor, while others reported that SRMs are the main mercury (Hg) methylators in freshwater systems. However, we have yet to fully explore how As(V) can affect methylmercury (MeHg) production. In this study, we examined whether additions of As(V) and sulfate in freshwater sediments collected near a major gold mine with a history of S and As emissions affect Hg methylation. First, we show that Hg methylation in lake sediments was primarily limited by carbon substrate availability rather than by that of sulfate as terminal electron acceptors. Then, under conditions where carbon is not limiting, sulfate addition to the system significantly increased Hg methylation rate constants. Finally, we show that MeHg production rates in sediments significantly decreased with increasing As(V) concentrations, regardless of the sulfate concentration amended to sediments. This work underscores the apparent antagonistic effects of As(V) on the one hand, and carbon and sulfate on the other hand on the kinetics of Hg methylation. Arsenic controls on Hg methylation are complex and a combination of direct impact on the methylators' fitness, the formation of As-bearing mineral phases affecting Hg bioavailability, or changes in the microbial community structures over increasing As concentrations should be the focus of additional investigations.

Coupled abiotic and biotic processes in the hyporheic zone, where surface water and groundwater mix, play a critical role in the biogeochemical cycling of carbon, nutrients, and trace elements in streams and wetlands. Dynamic hydrologic conditions and anthropogenic pollution can impact redox gradients and biogeochemical response, although few studies examine the resulting hydrobiogeochemical interactions generated within the hyporheic zone. This study examines the effect of hyporheic flux dynamics and anthropogenic sulfate loading on the biogeochemistry of a riparian wetland and stream system. The hydrologic gradient as well as sediment, surface water, and porewater geochemistry chemistry was characterized at multiple points throughout the 2017 spring-summer-fall season at a sulfate-impacted stream flanked by wetlands in northern Minnesota. Results show that organic-rich sediments largely buffer the geochemical responses to brief or low magnitude changes in hydrologic gradient, but sustained or higher magnitude fluxes may variably alter the redox regime and, ultimately, the environmental geochemistry. This has implications for a changing climate that is expected to dramatically alter the hydrological cycle. Further, increased sulfate loading and dissolved or adsorbed ferric iron complexes in the hyporheic zone may induce a cryptic sulfur cycle linked to iron and carbon cycling, as indicated by the abundance of intermediate valence sulfur compounds ( e.g. , polysulfide, elemental sulfur, thiosulfate) throughout the anoxic wetland and stream-channel sediment column. The observed deviation from a classical redox tower coupled with potential changes in hydraulic gradient in these organic-rich wetland and stream hyporheic zones has implications for nutrient, trace element, and greenhouse gas fluxes into surface water and groundwater, ultimately influencing water quality and global climate.

An efficient potassium persulfate-mediated radical addition of allenamides with diselenides was developed to create a workable route to 1,2-diselenide products. The reaction tolerates a wide spectrum of functional groups to deliver the products in good to excellent yields. Mechanistic investigations including a calculation study indicated that the radical cascade proceeds through a vinyl radical intermediate, which is formed via a selenium radical added to the terminal CC double bond of allenamides.

Sulphate and dissolved organic matter (DOM) in freshwater systems may regulate the formation of methylmercury (MeHg), a potent neurotoxin that biomagnifies in aquatic ecosystems. While many boreal lakes continue to recover from decades of elevated atmospheric sulphate deposition, little research has examined whether historically high sulphate concentrations can result in persistently elevated MeHg production and accumulation in aquatic systems. This study used sediment from a historically sulphate-impacted lake and an adjacent reference lake in northwestern Ontario, Canada to investigate the legacy effects of sulphate pollution, as well as the effects of newly added sulphate, natural organic matter (NOM) of varying sulphur content and a sulphate reducing bacteria (SRB) inhibitor on enhancing or inhibiting the Hg methylation and demethylation activity ( K meth and K demeth ) in the sediment. We found that K meth and MeHg concentrations in sulphate-impacted lake sediment were significantly greater than in reference lake sediment. Further adding sulphate or NOM with different sulphur content to sediment of both lakes did not significantly change K meth . The addition of a SRB inhibitor resulted in lower K meth only in sulphate-impacted sediment, but methylation was not entirely depressed. Methylmercury demethylation potentials in sediment were consistent across lakes and experimental treatments, except for some impacts related to SRB inhibitor additions in the reference lake sediment. Overall, a broader community of microbes beyond SRB may be methylating Hg and demethylating MeHg in this system. This study reveals that legacies of sulphate pollution in boreal lakes may persist for decades in stimulating elevated Hg methylation in sediment.

Food mediates susceptibility to inflammatory bowel diseases (IBDs) associated with the microbiome. Existing studies suggest that a high-sugar and high-fat diet promotes IBDs, but whether a plant-based diet is fully harmless to IBD improvement remains unknown. In this study, for the first time, we assessed the effect of soybean and its carbohydrates on dextran sodium sulfate (DSS)-induced colitis. In a DSS-induced colitis mouse model (BALB/C WT), the oral administration of soybeans worsened colitis, which was associated with higher disease activity index, histology score and expression of pro-inflammatory cytokines, and lower expression of anti-inflammatory cytokines. Here, 16S rRNA sequencing and elimination of gut bacteria by antibiotics showed that the exacerbating colitis caused by soybeans depends on the changes in the intestinal flora. Furthermore, the gavage of soybean carbohydrates such as sucrose and raffinose-family oligosaccharides altered the intestinal microbiota and worsened inflammation. When co-cultured with macrophages (RAW 264.7), the metabolites of the disordered intestinal flora, isolated Escherichia coli and purified LPS showed high macrophage toxicity to inhibit pathogen clearance. These results indicate that the intake of soybeans and soybean carbohydrates is not conducive to recovery from IBDs based on changes in gut microbiota and metabolites affecting the activities of macrophages.

Singlet oxygen refers to the nonradical metastable excited state of molecular oxygen that readily oxidizes various cellular components. Its behavior in different biological systems has been studied for many years. Recently, we analyzed the effect of singlet oxygen quenching by heme cofactor in cytochrome c (cyt c ). Here, we have exploited this effect in the investigation of conformational differences in the molten globule states of cyt c induced by different sodium anions, namely sulfate, chloride and perchlorate. The high efficiency of heme toward quenching singlet oxygen enabled us to use this property for the analysis of the otherwise experimentally difficult-to-determine parameter of heme upon exposure to solvents as highly similar conformational states of cyt c in the molten globule states are induced by different salts at acidic pH. Our results from singlet oxygen quenching experiments correlate well with other spectroscopic methods, such as circular dichroism and fluorescence measurements, and suggest increasing availability of heme in the order: perchlorate < chloride < sulfate. Based on our findings we propose that singlet oxygen phosphorescence measurements are useful in determining the differences in the protein conformation of their heme regions, particularly regarding the relative heme exposure to the solvent.

This study investigated the anti-inflammatory effects of cyanidin-3-glucoside (C3G) and blueberry pectin (BP) complexes on mice with dextran sodium sulfate (DSS)-induced colitis before and after high hydrostatic pressure (HHP) treatment. Real-time polymerase chain reaction (RT-PCR), western blotting, and 16S rDNA sequencing were used to study the expression of inflammation-related factors, activation of signal pathway-related proteins, and changes in the intestinal flora in ulcerative colitis (UC) mice. The results showed that HHP-treated C3G-BP complexes significantly relieved diarrhea and blood loss in the stool of UC mice and alleviated colon shortening. The potential mechanism of action involved reduction in intestinal oxidative stress mRNA expression of pro-inflammatory factors, improvement in anti-inflammatory factor levels, inhibition of the NF-κB signaling pathway, increased protein levels of Bcl-2/Bax and caspase-3/cleaved caspase-3 genes, and improved gut microbiota composition. Compared with other experimental groups, the HHP-treated C3G-BP complexes group exhibited the best anti-inflammatory effect on DSS-induced UC mice. The results may provide new ideas for using C3G-BP complexes for treating UC and help develop better processing methods.